CN101495309A - Retroreflective article comprising a copolyester ether composition layer and method of making same - Google Patents
Retroreflective article comprising a copolyester ether composition layer and method of making same Download PDFInfo
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- CN101495309A CN101495309A CNA2007800277031A CN200780027703A CN101495309A CN 101495309 A CN101495309 A CN 101495309A CN A2007800277031 A CNA2007800277031 A CN A2007800277031A CN 200780027703 A CN200780027703 A CN 200780027703A CN 101495309 A CN101495309 A CN 101495309A
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- Prior art keywords
- layer
- counter
- reflective products
- copolyester ether
- ground floor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Elements Other Than Lenses (AREA)
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Abstract
A retroreflective article that includes a first layer that includes a copolyester ether composition, and a second layer that includes a retroreflective structure juxtaposed in at least a partially overlying relationship to the first layer is disclosed. Also disclosed is a method of forming a retroreflective article that includes providing at least a copolyester ether composition layer, and providing a retroreflective structure in a juxtaposed and at least partially overlying relationship to the composition layer.
Description
The disclosure relates to counter-reflective products and preparation method thereof.More particularly, the disclosure relates to counter-reflective products that comprises copolyester ether composition layer and preparation method thereof.
Background technology
Counter-reflective products has the ability of the light of oblique incidence being led again the light echo source.The ability of this uniqueness has made counter-reflective products be widely used in the multiple substrate.For example, counter-reflective products can be used in the substrate (such as traffic sign and roadblock) of smooth, inflexibility; On the irregular surface (as corrugated metal trailer, car plate and traffic guardrail); And on the flexible substrates (as road maintenance workman's safety vest, running shoes, roll mark and canvas canopy truck).Counter-reflective products also is used for multiple other safety and ornamental purpose.Counter-reflective products is particularly useful under low light condition, and it returns incident light source and improve security by inciding light retrodirective reflection on it.
Counter-reflective products is used on the clothes usually, improves individual observability by the retrodirective reflection incident light.The counter-reflective products that is used on the clothes comprises: with heat sensitive adhesive adhere to band, the permanent attachment on the clothes or be sewn onto armband on the clothes and clothes in comprise the clothing item of counter-reflective products.The retrodirective reflection clothes are particularly useful to builder and the personnel that utilize the track to perform physical exercise, because these people are often near the vehicle that travels, and counter-reflective products makes that these people are easier under low light condition and seen by the driver.
Counter-reflective products is used as cover sheet with highly plasticized polyvinyl chloride (PVC) film usually, so that light propagates into the retroreflective structure that comprises (for example) cube-corner retroreflective element.Yet plasticizer tends to move from the PVC film.Therefore, in the course of time, the plasticized PVC film can lose temperature stability and flexibility (especially under the weather of cold).In addition, plasticizer is used for the flexibility of reinforced polyvinyl chloride (PVC) film.Yet plasticizer makes the PVC film show low relatively softening temperature (as 180).This low softening temperature tends to the commerce manufacturing of the counter-reflective products that comprises the plasticized PVC film is limited to some extent, and this is because the insufficient rigidity of plasticized PVC film is transmitted to carry out effective tablet by manufacture process.For example, the cube-corner retroreflective element can be cured under than the higher temperature of the softening temperature of PVC film when casting or joining on the plasticized PVC film usually.This softening in order to compensate, usually additional polyester layer is joined on the plasticized PVC film, these polyester layers (such as) be the top flat and the strippable backing sheet that under the solidification temperature of solid angle, can not soften.Though can carry out effective tablet transmission, these extra plays have increased the totle drilling cost of making, and therefore go out of use at last.In addition, the solid angle of casting need be annealed to the plasticized PVC film, to overcome the softening adverse effect that is brought after solidifying.Yet annealing will increase total manufacturing cost of energy.It is reported that dioctyl phthalate (DOP) waits some plasticizer to work the mischief to teen-age health.Also can produce other long durability problem when using the plasticized PVC film.
Summary of the invention
In one aspect, the disclosure comprises a kind of counter-reflective products, and it comprises the ground floor that comprises copolyester ether composition and the second layer that comprises retroreflective structure, wherein the second layer and ground floor and put and cover at least in part at least a portion of ground floor.
On the other hand, the disclosure comprises a kind of counter-reflective products, and it comprises ground floor that comprises copolyester ether composition and the second layer that comprises retroreflective structure, and wherein retroreflective structure bonding (bonded) is at least a portion of ground floor.
On the other hand, the disclosure comprises the method that forms counter-reflective products, and described method comprises: ground floor is provided, and this layer comprises copolyester ether composition basically; And, at least a portion top casting of ground floor and the resin combination of cure curable, so that the resin combination after solidifying forms retroreflective structure.
On the other hand, the disclosure comprises the method that forms counter-reflective products, and described method comprises: the film that comprises copolyester ether composition layer is provided; And at least a portion that makes this film contacts with curable resin combination and solidifies, so that resin combination forms retroreflective structure.
Present disclosure is not to be intended to describe each disclosed embodiment of the present disclosure or every kind of embodiment.Along with the expansion of describing, a plurality of other advantages, feature and relation will be apparent.The drawings and specific embodiments hereinafter more specifically illustrate exemplary embodiment of the present disclosure.By accompanying drawing and this specification, of the present disclosure above-mentioned apparent with other aspects general.Yet under any circumstance, above-mentioned aspect should not be understood that it is restriction to claimed theme, and this theme only is subjected to the qualification of appended claims, and can revise in course of the review.
Description of drawings
Fig. 1 is a kind of schematic cross sectional views of counter-reflective products, and these goods have the discrete cube-corner retroreflective component structure that is adhered to copolyester ether composition top flat or top layer.
Fig. 2 is the schematic cross sectional views of another kind of counter-reflective products, and these goods have the copolyester ether composition layer with another kind of polymer coextrusion, and described another kind of polymer has the retroreflective structure that is adhered to other polymer.
Fig. 3 is the schematic cross sectional views of another kind of counter-reflective products, and these goods have the polymeric layer and the copolyester ether layer of coextrusion, and wherein retroreflective structure is adhered to copolyester ether composition layer.
Fig. 4 has the brightness of counter-reflective products of the copolyester ether composition top flat of 5 mils and 8 mils or top layer and occupation that European standard EN471 lists with the high-visibility figure that the clothes luminance standard compares that reports to the police.
Fig. 5 is the figure of the brightness of counter-reflective products in 50 washings and 10 drying cycles processes of copolyester ether film composition with 6 mils (as the top layer of counter-reflective products).
Fig. 6 has the brightness of counter-reflective products of copolyester ether composition of 8 mils and the figure that luminance standard that European standard EN471 lists compares, and wherein uses described composition to impress under 425 conditions as the counter-reflective products of top layer.
Fig. 7 is the schematic diagram according to the manufacture method of counter-reflective products of the present disclosure.
Fig. 8 has the schematic cross sectional views based on a kind of counter-reflective products of the structure of microballoon that is adhered to copolyester ether composition layer.
Fig. 9 is the schematic cross sectional views that has based on another embodiment of the counter-reflective products of the structure of microballoon.
Figure 10 is the schematic cross sectional views that has based on another embodiment of the counter-reflective products of the structure of microballoon.
The specific embodiment
Word " a kind of ", " being somebody's turn to do " and " described " are used interchangeably with " at least one ", represent one or more described elements.When representing the position of various elements in the disclosed goods, we are meant the relative position of this element with respect to horizontally disposed main part by using the word (for example " top ", " covering ", " preceding " and " backing " etc.) of representing the orientation.We have no intention to make disclosed goods to have any specific spatial orientation in its manufacture process or after making.
Word " light " is meant the visible radiation in the electromagnetic spectrum.Two or more elements in relating to light path and when using term " optical correlation connection ", expression sees through described element along the major part of the light of described optic path.
" retrodirective reflection " goods make the incident light of oblique incidence along parallel with incident direction or almost parallel direction reflection, so that reverberation can be seen or detect to this light source place or observer or detector near it." transparent " reflective elements is meant, along measuring in the bandwidth of the 100nm at least of normal axis in the wave-length coverage of being paid close attention to of about 400nm between about 700nm, unidirectional transmitance is at least about 5% (and being preferably at least about 10%, 20% or 50%).
Two kinds of known types of counter-reflective products are based on the type of micro prism or solid angle and based on the type of microballoon.When using word " micro prism " when relating to counter-reflective products, typically refer to the solid angle element array.The cube-corner retroreflective element generally includes trihedral structure (being solid angle) and comes retrodirective reflection incident light, this structure to have three roughly orthogonal sides, and these sides intersect at single angle.Solid angle retrodirective reflection sheet material generally includes thin hyaline layer, this hyaline layer has flat basically front surface and structuring rear surface, this structuring rear surface comprises a plurality of geometries, and some or all of these geometries comprise three reflecting surfaces that constitute the cube-corner retroreflective element.
Use term when " based on microballoon " when relating to counter-reflective products, typically refer to have a large amount of microballoons or " pearl " (these microballoons or " pearl " embed in the adhesive layer usually at least in part) and have relevant minute surface reflection or diffuse-reflective material (for example granules of pigments, splint or vapour coating) with the sheet material of retrodirective reflection incident light.Therefore owing to contain the geometry that the pearl retro-reflector has symmetry, no matter its direction how, promptly when rotating around the axle perpendicular to sheet surface, all can demonstrate reflection fully to light based on the sheet material of microballoon.Therefore, this sheet material based on microballoon has low relatively sensitiveness to sheet material layout orientation from the teeth outwards.Yet in general, the retrodirective reflection efficient of this sheet material is lower than the retrodirective reflection efficient of cube comer sheetings.
Word " polymer " comprises homopolymers and copolymer and can or form (comprising (for example) ester exchange reaction) homopolymers or the copolymer of mixable blend by reaction by (for example) coextrusion.Term " copolymer " comprises atactic polymer and block polymer.Term " copolyester ether composition " comprises the compound of copolyester ether material and the blend of copolyester ether and other polymer.
Fig. 1 shows according to principle of the present disclosure usually by the embodiment of the counter-reflective products of reference number 10 expression.In this embodiment, counter-reflective products 10 comprises layer or retroreflective structure 12.Retroreflective structure 12 generally includes generally flat surface 14 and the retrcreflective surface 16 watched.In this embodiment, the generally flat surface 14 of watching is adhered on the generally flat surface of copolyester ether composition layer 20 usually.
Cube-corner retroreflective element 18 can prepare by being cast straight on the film, as U.S. Patent No. 5,691, described in 846 (Benson) like that, this patent is incorporated this paper into way of reference.The typical polymers that is used for the cube-corner retroreflective element of radiation curing include, but is not limited to crosslinked acrylate (for example polyfunctional acrylic ester or epoxy resin) and with the acrylate modified polyurethane of monofunctional monomer and polyfunctional monomer blend.Other typical polymers that are used for the cube-corner retroreflective element include, but is not limited to: Merlon, polymethyl methacrylate, PETG, aliphatic polyurethane, polyvinyl chloride, ethylene copolymer and ionomer thereof.
Adopt at counter-reflective products under the situation of cube comer sheetings,, can have protective layer in order to prevent chemistry and/or ultraviolet degradation.Based on the illustrative examples of the retrodirective reflection sheet material of solid angle in U.S. Patent No. 5,138,488 (Szczech), No.5,387,458 (Pave lka), No.5,450,235 (Smith), No.5,605,761 (Burns), No.5,614,286 (Bacon) and No.5,691,846 (Benson, Jr.) have disclosedly in, these patents are all incorporated this paper into way of reference.May be exposed among the embodiment of moisture at sheet material, the solid angle reflective elements is preferably sealed with the diaphragm seal (not shown).The usual manner of attached diaphragm seal includes, but is not limited to: RF welding, ultrasonic bonding, hot adhesion or Sealing Method and other known appropriate methodologies.In use, retroreflective structure 12 is arranged in such a way: watch surface (promptly watch surface 14) roughly to be provided with towards the desired location of expection observer and incident light source before it.Watch the light on the surface 14 to enter sheet material and pass sheet body before inciding, by each face reflection in three faces of reflecting element, thereby along leaving front surface towards the direction of incident light source basically.Under the situation of total internal reflection, the air interface (not shown) must keep free from dust, anhydrous and adhesive-free, is therefore sealed by diaphragm seal.Light is reflected in the side because of total internal reflection usually, or is reflected by the reflectance coating on the back side of side.
Copolyester ether composition layer 20 can be made by any suitable light transmissive copolyester-ether elastomers.Typical example comprises cyclohexanedimethanol, 1,4-butanediol and terephthalic acid (TPA).Should be appreciated that can commercially available other suitable copolyester ether compositions.Be used for realizing that the more typical elastomer of enhanced retroreflective article is that (Kingsport Tennessee) makes by Eastman Chemical Company
FN006.Fundamentally, this FN006 elastomeric material looks like based on poly-(oxolane)-the be also referred to as copolyester ether mixture of poly-(1, the 4-butanediol).Poly-(1, the 4-butanediol) exists as independent molecule in copolymer, or has considerable time in copolymer.The cis-1 in addition that identifies, 4-cyclohexanedimethanol and anti-form-1,4-cyclohexanedimethanol and 1,4-butanediol and anti-form-1, the copolymer of 4-cyclohexane dicarboxylic acid.Aromatic compounds and/or other compounds that can have trace.
Following table 1 has been listed FN006 
Composition:
| Material | Integrated value (Integral) | Multiple (Mult) | Mol ratio | Mole % | Molecular weight | Quality % |
| Poly-(1, the 4-butanediol) | 62.48 | 4 | 15.62 | 37.75％ | 90.12 | 26.04％ |
| 1, the 4-cyclohexane dicarboxylic acid | 25.27 | 2 | 12.64 | 30.54％ | 172.15 | 40.25％ |
| Anti-form-1, the 4-cyclohexanedimethanol | 32.77 | 4 | 8.19 | 19.80％ | 144.21 | 21.86％ |
| Cis-1, the 4-cyclohexanedimethanol | 14.53 | 4 | 3.63 | 8.78％ | 144.21 | 9.69％ |
| 1, the 4-butanediol | 5.19 | 4 | 1.30 | 3.14％ | 90.12 | 2.16％ |
The variations that other phase Sihes of disclosure expection copolyester ether composition are fit to can be used under the situation of the practice that meets disclosure principle.For example, the common variations of said composition comprises the form of their variation of MW (molecular weight) in about plus or minus 10% scope.Also can expect the variations that other are fit to.
Copolyester ether composition layer 20 is substantially free of plasticizer, and is transparent for the light that passes.As used herein, the amount that term " is substantially free of plasticizer " represents the plasticizer that it contains can not impair and not contain the benefit that any plasticizer produces.Therefore, copolyester ether composition film is not subject to the influence of problem due to the migration of plasticizer, for example is not subjected to the influence of the problem due to the plasticized PVC.Described problem includes, but is not limited to: lose flexibility, lose heat endurance and wearing and tearing too early.In addition, copolyester ether composition layer has the softening temperature more than 400.Therefore, in the casting and solidification process of counter-reflective products, do not need to facilitate for its tablet transmission for copolyester ether composition layer adds extra play.
The top layer of counter-reflective products 10 or copolyester ether composition layer 20 also can comprise the film of the blend that contains copolyester ether component and a selected amount of at least another kind of polymers compositions (as copolyester).For concrete application, can add other polymer to strengthen or to improve the characteristic of copolyester ether composition.Other suitable polymers can be used as resin adds in the copolyester ether resin, and is sheet material by coextrusion.In the embodiment of a blend, first component that accounts for the copolymer polyester resin of the maximum 25 weight % of gross weight can be added in the copolyester ether resin, with the intensity of increase top layer 20, and can the characteristic of copolyester ether composition layer not had a negative impact.Alternatively, in the composition of two kinds of other blend, can add accounting for the copolymer polyester resin of the about 5 weight % of gross weight to about 95 weight %.On the contrary, in a kind of blend in back, the ratio of copolyester ether resin complementally accounts for about 95 weight % of gross weight to about 5 weight %.Also can expect other blend and blending ratio.
Advantage of the present disclosure is, copolyester ether composition layer has following feature, promptly its approximately-100 °F to about 400 wide temperature range, demonstrate temperature stability.The fusing point of copolyester ether composition layer is higher than 400 °F, and copolyester ether composition film just can become frangible in time below-100.Therefore, copolyester ether composition layer can use (especially outdoor utility) in the temperature conditions of wide region, can not cause performance significantly to reduce because of extreme temperature.In addition, because its softening temperature is higher, so copolyester ether composition layer can pass through that firing equipment (as heating iron) directly engages and non-degradable.Counter-reflective products with copolyester ether composition layer is multiduty, especially with respect to this based article that adopts the plasticized PVC film.The situation of the migration of plasticizer can not take place in the copolyester ether composition layer in addition, basically.
The thickness of copolyester ether composition top layer 20 mostly is about ten (10) mils usually most.More typically, the thickness of copolyester ether composition top layer 20 can be in about 0.2 mil between 8 mils.Copolyester ether composition film can be used as copolyester ether composition top layer 20 or another layer of counter-reflective products 10, because copolyester ether composition or film top layer 20 be heat-staple, ambient stable, visually transparent, antifouling, be easy to from instrument or mould, break away from, and be easy to admit reflectance coating (as discrete cube-corner retroreflective element).Because therefore the intrinsic physical characteristic and the thermal characteristics of copolyester ether composition film layer 20 need not to add additional sheet material (as top flat and backing thin slice) on copolyester ether composition film in solidifying the solid angle process.In addition, this will reduce the required layer of commodity production counter-reflective products 10 or the quantity of carrier film, thereby save great amount of cost.
With reference to figure 7, it shows an exemplary embodiments of the system of processing 700 that is used to prepare counter-reflective products as shown in Figure 1.In this regard, should be appreciated that and have multiple device and the system that is suitable for preparing counter-reflective products.For example, refer again to U.S. Patent No. 5,691,846, it has been described in the film top casting and has solidified the cube-corner retroreflective element to prepare the method for counter-reflective products.In the system of processing 700 that is used for making counter-reflective products of the present disclosure, runny curable resin combination 710 is used in copolyester ether composition layer 721 top castings and is solidified into cube-corner retroreflective element 719.Copolyester ether composition layer 721 is pulled by the driving mechanism (not shown) of patterned tool 726 from withdrawal roller 722 along a paths (for example) or is advanced.Composition layer 721 can be flexible, ductile thin slice.Along with advancing of composition layer 721, curable resin combination 710 is applied on the composition layer 721 after coating die 725 applies.The typical polymers that curable resin combination 710 can comprise includes, but is not limited to: Merlon, polymethyl methacrylate, PETG, aliphatic polyurethane, polyvinyl chloride and ethylene copolymer and ionomer thereof.More typical curable resin combination 710 is the UV gel-type resin, such as epoxy acrylate, urethane acrylate and simple function, difunctionality and polyfunctional acrylate monomer (for example can from being positioned at Smyrna, those that the Cytec SurfaceSpecialties of Georgia is commercially available).
The curable resin combination 710 that has applied is transported to patterned tool 726, and resin combination 710 enters in a plurality of microcavitys 727 on the patterned tool 726 by roll 723 (as the roller of coating rubber) and patterned tool 726 at this.Composition layer 721 contacts with resin combination 710 in the microcavity 727.As shown in the figure, paired UV ray radiation source 729 (for example uviol lamp) is arranged to the composition 710 that comes radiation curable with the mode of 721 one-tenth certain distances of advancing composition layer.When contacting with composition layer 721, curable resin combination 710 is cured or is partly solidified, to form the array of bonding cube-corner retroreflective element 719.Composition layer 721 is transparent for the photochemical UV ray radiation source from UV ray radiation source 729.In this regard, used term " transparent " expression composition layer 721 must be able to allow the ray of effective ratio therefrom pass.In this embodiment, radiation source 729 is with the curable resin combination of required ultraviolet radiation wavelength illumination, effectively to solidify.Roll 728 be responsible for solidifying or partly solidified cube-corner retroreflective element 719 with patterned tool 726 disconnections or peel off, thereby make the cube-corner retroreflective element when take up roll 731 advances in driving mechanism (not shown) by patterned tool 726, they are adhered on the composition layer 721, and transmit with composition layer 721.Cube-corner retroreflective element 719 can separately become discrete component.In addition, second similar to paired radiation source 729 UV ray radiation source 730 is used to finish curing.Alternatively, U.S. Patent No. 5,691,846 describe and have instructed the method for formation cube comer sheetings (rather than independently solidifying reflecting element).For example, can directly curable resin combination 710 be applied on the microcavity 727.
The cube-corner retroreflective element can be the type that is exposed to air of opening wide, the type of sealing or metallized type.
The advantage of system of processing 700 is from having the high softening temperature composition layer 721 of (as more than 400), thereby do not need to do, in the whole manufacturing process of counter-reflective products, adopt extra play to help composition layer as being generally the counter-reflective products that (for example) have the plasticized PVC film.In addition, owing to do not meet or exceed the softening temperature of composition layer 721, thereby do not need annealing.Therefore, system of processing 700 is characterised in that, compares with the manufacture method of the known counter-reflective products with plasticized PVC film, and it has improved economic effect and has simplified.
Referring to Fig. 2, the figure shows another kind of retroreflective structure 100, this structure comprises copolyester ether composition layer 102, said composition layer and intermediate layer 104 coextrusion another kind of at least and that put and cover to small part copolyester ether composition layer 102.Intermediate polymer layer 104 is formed by polymer (more particularly, polyurethane or copolyester material) usually.Retroreflective structure 106 (typically being solid angle array) is adhered on the intermediate polymer layer 104.Intermediate polymer layer 104 makes light transmission, to realize the optical correlation connection between composition layer 102 and the retroreflective structure 106.Intermediate polymer layer 104 can be adhered on the composition layer 102 by the such mode of radiation curing or by other typical methods.Intermediate polymer layer 104 can be made by any material in the number of suitable materials that is commonly used to prepare counter-reflective products.For example, intermediate polymer layer 104 and other such layers can comprise other material and improve the retrodirective reflection optical property of counter-reflective products and/or other functions are provided.Reflective metal layer 108 adheres on the retroreflective structure 106, and optional responsive to temperature type adhesive phase or pressure sensitive adhesive layer 110 (for example polyurethane, acrylic resin, rubber or other hotmelts) can adhere on the reflective metal layer 108.Because the temperature stability of copolyester ether composition layer 102, therefore can thermal source is disposed thereon, so that enough heat to be provided, make adhesive phase 110 softening on the substrate (not shown) such as fabric that is fit to, and can not cause damage or the counter-reflective products that has applied is caused adverse effect.
Referring to Fig. 3, the figure shows another example of counter-reflective products 200.Counter-reflective products 200 can comprise the copolyester ether composition layer 202 with another polymeric layer 204 coextrusion.By curable and runny resin combination (as acrylate) being applied in a known way on the typical patterned tool that retroreflective structure 206 is bonding or be cured on the copolyester ether composition layer 202.Described resin is cured on the copolyester ether composition layer 202, to form the cube-corner retroreflective element arrays of retroreflective structure.Counter-reflective products 200 can be used in the following situation: the inside of counter-reflective products 200 need have hear resistance, and outer surface does not need to have hear resistance.Though the counter-reflective products that illustrates has two to five layers, the disclosure also contains and has six layers or more multi-layered counter-reflective products.
Following example is exemplary, and its purpose is not to limit the disclosure by any way.
Example 1
Tested the intrinsic mechanical properties of film of the blend of the copolyester ether composition layer of 5 mils or film and 6 mils, the composition of the film of described blend comprises the component of the copolyester of the component of copolyester ether of about 90 weight % and about 10 weight %.The two all is that (Kingsport Tennessee) makes, and wherein copolyester ether composition is with trade name FN006 by Eastman ChemicalCompany
Sell.With the two and Achilles USA, (Everett, Washington) (AuburnHills, Michigan) polyurethane film of 4 mils of Zhi Zaoing and 10 mils compares Inc. for the plasticized PVC film of 7.25 mils of Zhi Zaoing and Huntzman LLC.Each that will be except that the polyurethane of 10 mils " is purchased " rectangle that film all is cut into 1 inch * 4 inches, and it is 0.6 to 0.75 inch that the polyurethane of 10 mils is cut into width, and length is 4 inches.
Use is tested each sample by the step of ASTM D882 " standard test method of sheet plastic material tensile properties " (Standard Test Method of Tensile Properties of Thin PlasticSheeting) definition.Employing is by MTS SystemsCorporation (Minneapolis, Minnesota) the Testworks V DAQ tester of Zhi Zaoing and by MTS Systems Corporation (Minneapolis, Minnesota) the Alliance 100 single shaft testers (Alliance 100uniaxial tester) of Zhi Zaoing are determined the distortion of load displacement collection value and stress-strain.All tests are all carried out under environmental condition.Gather in the test result table 2 below.
Table 2
| Sample | Peak stress (MPa) | Breaking tension (%) | Young's modulus (MPa) | Energy to fracture (joule) | Yield strain (%) |
| Hunt zman 4 mil PU 1 | 29 ±8 | 722 ±101 | 7 ±2 | 13 ±4 | 75 ±11 |
| Huntzman 10 mil PU 1 | 22 ±5 | 563 ±103 | 10 ±2 | 15 ±5 | 50 ±15 |
| Achilles 7.25 mil PVC 2 | 26 ±1 | 343 ±17 | 52 ±5 | 15 ±1 | 27 ±2 |
| The Neostar blend 36 mils | 36 ±3 | 390 ±40 | 230 ±20 | 18 ±3 | 23 ±4 |
| Neostar 45 mils | 23 ±3 | 630 ±110 | 120 ±15 | 15 ±4 | 36 ±3 |
The 1PU=polyurethane film
2PVC=plasticised polyvinyl chloride film
3.
The copolyester film of the copolyester ether of blend=90 weight %/10 weight %
4.
=copolyester ether film
The result of these tests shows that the energy to fracture of five (5) individual specimen does not have the marked difference on the statistical significance.Statistical analysis shows, the characteristic overlaid of whole four significant differences of the characteristic of neither one sample and PVC sample in the non-PVC sample.Yet the Young's modulus value of copolyester ether film composition (5 mil) and copolyester ether/copolyester blend (6 mil) film is higher than the Young's modulus value of PVC sample and polyurethane samples.
Adopt TAIQ800 series dynamic mechanical analysis instrument (DMA) (TAIQ800seriesDynamic Mechanical Analyzer), the mode that stretches with film, utilize 15 microns swing peak to the strain rate (frequency) of peak strain amplitude and 1 hertz, under-112 to 212 temperature, test this five kinds of membrane samples respectively with about 4.24/minute speed.Gather in DMA result's table 3 below.
Table 3
DMA result
| Sample | E ' in the time of 24 ℃ 5 (MPa) | Rigidity in the time of 24 ℃ (N/m) | Tg 6(calculating) by Tan σ maximum (℃) |
| Huntzman PU 1(4 mil) | 24 | 1315 | -15 |
| Huntzman PU 1(10 mil) | 22 | 2580 | -17 |
| Achilles PVC 2(7.25 mil) | 228 | 19,200 | 35 |
| The Neostar blend 3(6 mil) | 496 | 32,500 | 27,67 |
| Neostar 4(5 mil) | 230 | 12,800 | 3 |
1.PU=polyurethane film
2.PVC=plasticised polyvinyl chloride film
3.
The copolyester film of the copolyester ether of blend=90 weight %/10 weight %
4.
=copolyester ether film
5. storage modulus
6. glass transition temperature
The result of these tests shows two
The plasticized PVC film of the mechanical property of sample and 7.25 mils is the most suitable, and their storage modulus value is greater than the storage modulus value of plasticized PVC film.Test shows copolyester ether film and copolyester ether/copolyester film blend can be the suitable substitute of plasticised polyvinyl chloride film.
Example 2
Adopt the C2001 acrylate (by being positioned at Smyrna, the CytecSurface Specialties manufacturing of Georgia) handles five (5) mil film and eight (8) mil copolyester ether composition film (by Eastman Chemical Company (Kingsport, Tennessee) make, trade mark is
), cast and solidify duplicate by the nickel mould that mainly is spaced apart 7.0 mils.Use Fusion UV Systems, (Gaithersburg, Maryland) the ultraviolet deuterium lamp of Zhi Zaoing is being set under about 60% the condition of its peak power acrylate curing and it is attached on the film on the nickel patterned mold Inc..During test, film is advanced with the linear velocity of about 20 feet per minute clocks.
The cohesive of acrylate and copolyester ether composition film is by the solid angle retroreflective structure being marked, utilized then band (adopt 3M company (St.Paul, Minnesota) 898 cord belts of Zhi Zaoing) speed to draw the adhesion method of testing to test.The cohesive of acrylate and copolyester ether composition film has been passed through the adhesion test, tests brightness, wash adhesion and the temperature performance of counter-reflective products subsequently.
Adopt EN471 European standard " method of testing and requirement that occupation is reported to the police and obeyed with high-visibility " (High-visibility warning clothing for professional use-Testmethods and Requirements) to come test brightness.The results are shown in Figure 4, the result shows that the brightness of copolyester ether/acrylate retrodirective reflection composition is equal to or greater than the standard that the desired occupation of European standard EN471 is reported to the police and obeyed with high-visibility.
In about 60 ℃ of following cyclic washing copolyester ether/acrylate counter-reflective products and dry repeatedly retroreflective structure is tested the copolyester ether/acrylate counter-reflective products under about 50 ℃ durability.The result as shown in Figure 5, the result shows in 50 cycles of washing and 10 drying cycles (carrying out drying cycles 1 time after per 5 continuous cycles of washing) afterwards, although the copolyester ether/acrylate counter-reflective products has degraded to a certain degree, but still keep about 25% of its original intensity.After 50 washings and drying cycles, no cube-corner retroreflective element breaks away from copolyester ether composition film.Two tests show that all copolyester ether composition film is the suitable thin slice that is used for such counter-reflective products, and described counter-reflective products is need to be used to the clothes of cyclic washing and protection or other application.Though bound by theory not it is believed that washing can make brightness reduce, this is because the contact between the discrete cube-corner retroreflective element causes.Range estimation shows that discrete solid angle sticks on the copolyester ether composition film perfectly.
(Pittsburg, Kansas) the N-80 hot press of Zhi Zaoing is tested the high-temperature stable characteristic of the copolyester ether/acrylate counter-reflective products of 8 mils, and compares with the situation of using plasticized PVC to adopt Hix Corporation.Hot press is used under the pressure of about 425 temperature, about 20psig, flashing pattern is printed off in hot pressing on each film in about 50 seconds time.The fusion of PVC film also is bonded to stamping surface, does not therefore measure its brightness.The copolyester ether/acrylate counter-reflective products at high temperature impresses, and has brightness reading as shown in Figure 6, and described brightness reading is similar to the brightness reading of the not copolyester ether/acrylate retroreflective structure of impression shown in Figure 4.Another advantage of this retroreflective structure is that it can stand higher temperature than the retroreflective structure of plasticized PVC type, and can not lose its stability.
Fig. 8 shows the counter-reflective products that comprises copolyester ether composition layer 802 or an embodiment of film 800, and the said composition layer is adhered on the surface based on the retroreflective structure 830 of microballoon.That describes among copolyester ether composition layer 802 and the front embodiment is similar, and can carry out bonding or attached in any suitable manner.After adopting the said method institute similar method relevant with Fig. 7 to form retroreflective structure 830, copolyester ether composition layer 802 can add on this retroreflective structure.A kind of typical types that can adopt based on the retroreflective structure 830 of microballoon at United States Patent (USP) 6,677, have disclosed among 028 (Lasch).Specifically, retroreflective structure 830 comprises having watches surface 813 suitable surface element 833, a plurality of Transparent bead 822 and suitable reflecting layer 824, and this reflecting layer remains on co-location place with respect to pearl by adhesive layer 835.Adhesive phase 837 joins on the reflecting layer 824.Transparent bead 822 has first hemispherical portion of being sealed by surface element 833 and is arranged in second opposed hemispherical part adhesive layer 835, that separate with reflecting layer 824.That the disclosure has been conceived is spendable, typically based on the alternative form of micro-sphere structure.These alternative forms include, but is not limited to U.S. Patent No. 4,025,159 (McGrath), No.4,983,436 (Bailey), No.5,064,272 (Bailey), No.5,066,098 (Kult), No.5,069,964 (Tolliver), No.5,262,225 (Wilson) and No.5, those that describe among 812,317 people such as () Billingsley.
Fig. 9 shows the embodiment that embodies exposed lens type of microsphere retroreflective article 900 of the present disclosure.Counter-reflective products 900 comprises the optical element of the form of 916 layers of microballoons at least and specular layer 917.Contain in the pearl structure at this, 916 layers of microballoons are spherical in shape basically, so that uniform retrodirective reflection to be provided.Though the specular layer 917 that illustrates contacts with microballoon, and so nonessential, can use the intermediate layer (not shown) because be known that.In this embodiment, 916 layers of microballoons and specular layer 917 can be suitably and juxtaposed copolyester ether composition layer 918 coextrusion, and to form counter-reflective products 900, wherein microballoon becomes the form that is embedded in the copolyester ether composition layer 918 for 916 layers.Though copolyester ether composition layer 918 is coextruded to 916 layers of microballoons and specular layer 917, disclosure expection can be coated with copolyester ether composition layer 918 by other suitable coating processes.A kind of typical method of preparation counter-reflective products 900 is described among 998 people such as () Tung to some extent in U.S. Patent No. 4,377.Yet main difference is that copolyester ether composition layer 918 has replaced the binder layer material described in this patent.In this regard, copolyester ether composition layer 918 has foregoing high melting temperature, so it is heated to a certain degree so that it is softening, thereby in counter-reflective products 900 forming processes, microballoon 916 will be partially submerged in the said composition layer.Therefore encapsulated lens microballoon counter-reflective products 900 is provided.
Figure 10 shows another embodiment of exposed lens type of retroreflective article 1000.The counter-reflective products of describing in counter-reflective products 1000 and the U.S. Patent No. 5,055,347 (Bacon) is similar, and it is described the part that content is used as this paper and incorporates this paper into.More particularly, counter-reflective products 1000 comprises 1016 layers of microballoons, specular layer 1017, adhesive layer 1018 and copolyester ether composition layer 1019 at least.Typically microballoon 1016 and specular layer 1017 are above-mentioned those.Layer 1016,1017 and 1018 more typical type be in U.S. Patent No. 5,055, describes to some extent in 347, and this is described the part that content is used as this paper and incorporates this paper into.In this embodiment, adhesive layer 1018 can comprise and can vulcanize or curable elastomer, and microballoon can embed wherein for 1016 layers thus.Adhesive layer 1018 has high melt temperature (for example, enough high to be used to the clothes of preventing fires).In following an exemplary embodiments of above-mentioned generation type, copolyester ether composition layer 1019 is coextruded to adhesive layer 1018 in known manner.Other coating processes have also been conceived to be used to prepare multi-ply construction.For example, counter-reflective products 1000 can (by sewing up) be attached to the fire prevention clothes.Alternatively, counter-reflective products 1000 these embodiment also imagine and comprise adhesive phase 1020, and this layer is adhered on the outward surface of copolyester ether composition layer 1019.Adhesive phase 1020 can comprise being intended to be heated and being applied to and be fit on the substrate (not shown) counter-reflective products 1000 is attached to this suprabasil any suitable hotmelt.The hotmelt that should be pointed out that selection should be its softening temperature and can not cause microballoon to sink in the copolyester ether composition layer 1018 for 1016 layers.As long as these layers can provide counter-reflective products 1000 required characteristic, the thickness of each layer can change.
All lists of references that comprise patent that this paper quotes clearly in full way of reference incorporate in the disclosure.The exemplary embodiment that the disclosure relates to has been discussed, and has been related to possible modification in the disclosure scope.Under the prerequisite that does not break away from the scope of the present disclosure, these forms of the present disclosure and other versions and modification will be conspicuous for a person skilled in the art; And should be appreciated that the disclosure is not limited to the exemplary embodiment that this paper provides.Therefore, the disclosure only is subjected to the restriction of appending claims.
Claims (29)
1. counter-reflective products, it comprises: comprise the ground floor of copolyester ether composition and comprise the second layer of retroreflective structure, described ground floor is put and covered at least in part to the described second layer and described ground floor also.
2. counter-reflective products according to claim 1, wherein said retroreflective structure comprises the micro prism structure.
3. counter-reflective products according to claim 1, wherein said retroreflective structure comprises the structure based on microballoon.
4. counter-reflective products according to claim 3, wherein said structure based on microballoon comprise at least and expose lens-type microballoon layer.
5. counter-reflective products according to claim 4, the wherein said lens-type microballoon layer segment ground that exposes embeds and to comprise in the described ground floor of described copolyester ether composition.
6. counter-reflective products according to claim 4, wherein said exposing during lens-type microballoon layer segment ground embeds the 3rd layer, and described the 3rd layer is adhered to the described ground floor that comprises described copolyester ether composition layer.
7. counter-reflective products according to claim 3, wherein said structure based on microballoon comprises the microballoon layer of sealing at least.
8. counter-reflective products according to claim 1, wherein said ground floor is substantially free of plasticizer.
9. counter-reflective products according to claim 1, wherein said ground floor has temperature stability in the temperature range between-100 to 400 approximately.
10. the described counter-reflective products of claim 1, the brightness of described counter-reflective products are equal to or higher than occupation that European standard EN 471 sets with the report to the police luminance standard of clothes of high-visibility.
11. counter-reflective products according to claim 1, wherein said ground floor comprises the copolyester ether compound at least.
12. counter-reflective products according to claim 1, wherein said ground floor comprises such blend, and described blend comprises first component that contains the copolyester ether compound and at least the second component that contains polymeric material.
13. counter-reflective products according to claim 1, the thickness of wherein said ground floor are about 10 mils to the maximum.
14. counter-reflective products according to claim 13, the thickness of wherein said ground floor is between about 0.2 mil and about 10 mils.
15. counter-reflective products according to claim 1 also comprises at least the three layer that comprises polymeric material, described the 3rd layer be adhered in the described ground floor and the described second layer at least one and be positioned in the middle of the described juxtaposed ground floor and the second layer.
16. counter-reflective products according to claim 1 also comprises at least the three layer that comprises polymeric material, described the 3rd layer of relative with the described second layer surface of watching that is adhered to described ground floor.
17. counter-reflective products according to claim 1, the blend that wherein said copolyester ether composition comprises comprise the composition of the copolyester of the copolyester ether of about 90 weight % and about 10 weight %.
18. counter-reflective products according to claim 1, wherein said micro prism structure are the array of cube-corner retroreflective element.
19. counter-reflective products according to claim 1, wherein said copolyester ether composition comprise the blending ratio of copolyester ether and copolyester be about 95 weight % to about 5 weight % than the composition of about 5 weight % to about 95 weight %.
20. a method that forms counter-reflective products comprises:
Copolyester ether composition layer is provided at least; With
Provide with described composition layer and put and cover the retroreflective structure of described composition layer to small part.
21. method according to claim 20, also comprise and provide the 3rd layer that contains polymeric material, described the 3rd layer is adhered in described composition layer and the described retroreflective structure at least one, thereby makes described the 3rd layer of centre that is positioned at described composition layer and described retroreflective structure.
22. method according to claim 20 also comprises providing at least the three layer that comprises polymeric material, described the 3rd layer of that be adhered to described composition layer and described retroreflective structure are opposing watches the surface.
23. method according to claim 20 also comprises being adhered to described composition layer with described composition layer and putting and cover at least in part on the described retroreflective structure of described composition layer.
24. method according to claim 20, the wherein said retroreflective structure that provides is the structure based on microballoon.
25. method according to claim 24, wherein said structure division ground based on microballoon embeds in the described ground floor.
26. method according to claim 24 is during wherein said structure division ground based on microballoon embeds the 3rd layer.
27. method according to claim 26 wherein is applied to described ground floor described the 3rd layer.
28. method according to claim 20, the wherein said retroreflective structure that provides is the micro prism structure.
29. a method that forms counter-reflective products comprises:
Copolyester ether composition layer is provided at least;
Curable resin combination is contacted, so that described curable resin combination forms retroreflective structure when solidifying with at least a portion of described composition layer; With
Solidify the described curable resin combination on the described composition layer, to form described retroreflective structure and it is adhered on the described composition layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/460,749 US7842374B2 (en) | 2006-07-28 | 2006-07-28 | Retroreflective article comprising a copolyester ether composition layer and method of making same |
| US11/460,749 | 2006-07-28 | ||
| PCT/US2007/073196 WO2008014115A1 (en) | 2006-07-28 | 2007-07-11 | Retroreflective article comprising a copolyester ether composition layer and method of making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101495309A true CN101495309A (en) | 2009-07-29 |
| CN101495309B CN101495309B (en) | 2012-08-29 |
Family
ID=38981789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800277031A Expired - Fee Related CN101495309B (en) | 2006-07-28 | 2007-07-11 | Retroreflective article comprising a copolyester ether composition layer and method of making same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7842374B2 (en) |
| EP (1) | EP2046576B1 (en) |
| JP (1) | JP5102295B2 (en) |
| KR (1) | KR101401716B1 (en) |
| CN (1) | CN101495309B (en) |
| TW (1) | TW200815797A (en) |
| WO (1) | WO2008014115A1 (en) |
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| JP6074128B2 (en) * | 2010-04-15 | 2017-02-01 | デクセリアルズ株式会社 | Optical body and manufacturing method thereof, solar shading member, window material, interior member and fitting |
| KR101281153B1 (en) * | 2011-05-24 | 2013-07-02 | (주)에스시아이 | The road sign reflector and its manufacturing method |
| CN103971610A (en) * | 2013-01-30 | 2014-08-06 | 宁波大红鹰学院 | Fluorescent traffic safety sticker with cartoon patterns |
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| JP6510318B2 (en) * | 2015-05-14 | 2019-05-08 | スリーエム イノベイティブ プロパティズ カンパニー | Graphic film for license plate, and license plate including graphic film and method of manufacturing the same |
| US10723299B2 (en) * | 2017-05-18 | 2020-07-28 | Srg Global Inc. | Vehicle body components comprising retroreflectors and their methods of manufacture |
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- 2007-07-11 JP JP2009521887A patent/JP5102295B2/en not_active Expired - Fee Related
- 2007-07-11 KR KR1020097001581A patent/KR101401716B1/en active IP Right Grant
- 2007-07-11 EP EP07799471.3A patent/EP2046576B1/en not_active Not-in-force
- 2007-07-11 CN CN2007800277031A patent/CN101495309B/en not_active Expired - Fee Related
- 2007-07-27 TW TW096127600A patent/TW200815797A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP2046576B1 (en) | 2013-05-01 |
| EP2046576A1 (en) | 2009-04-15 |
| JP2009545009A (en) | 2009-12-17 |
| EP2046576A4 (en) | 2012-04-18 |
| KR20090033455A (en) | 2009-04-03 |
| US7842374B2 (en) | 2010-11-30 |
| KR101401716B1 (en) | 2014-06-19 |
| TW200815797A (en) | 2008-04-01 |
| WO2008014115A1 (en) | 2008-01-31 |
| CN101495309B (en) | 2012-08-29 |
| US20080026184A1 (en) | 2008-01-31 |
| JP5102295B2 (en) | 2012-12-19 |
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